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Why is there a molecular relativistic effect?
Author(s) -
Katriel J.,
Feller D.,
Davidson E. R.
Publication year - 1984
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560260407
Subject(s) - valence (chemistry) , molecular orbital , wave function , atomic orbital , atomic physics , relativistic quantum chemistry , orthogonality , chemistry , molecular orbital theory , valence bond theory , slater type orbital , physics , quantum mechanics , molecule , geometry , electron , mathematics
The almost exclusive association of the molecular geometry dependence of the relativistic correction with the valence orbital contribution to the mass‐velocity and Darwin terms is investigated using SCF and MCSCF wavefunctions. The requirement of orthogonality of the valence orbitals to the core orbitals is confirmed to be the mechanism responsible for the increase in (the absolute value of) relativistic energy upon decrease of the internuclear distance. Certain “fingerprint”‐type features of the valence relativistic correction, revealing the identity of the particular core orbital giving rise to it, are identified.